Phenyl carbamates

ABSTRACT

O-Phenylcarbamates, e.g., those of the formula R1 H, alkyl or alkenyl R2 alkyl or alkenyl R3, 4 alkyl, alkenyl, alkynyl R3+R4 alkylene or alkenylene X1,2 H, aliphatic radical, halogen or nitro X3 O or S are biocides, e.g., insecticides.

States Patent [191 Niltlles et al.

[ Dee. 24., 197% 1 i PHENYL CARBAMATES [75] Inventors: Erwin Nikles, Liestal; Volker Dittrich; Ladislaus Pinter, both of Basel, all of Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Oct. 1, 1973 [21] Appl. N0.: 402,650

Related US. Application Data [60] Division of Ser. No. 197,474, Nov. 10, 1971, Pat. No. 3,781,301, which is a continuation of Ser. No. 2,445, Jan. 12, 1970, abandoned, which is a continuation-impart of Ser. No. 728,335, May 13, 1968, abandoned, which is a division of Ser. No. 493,256, ()cl. 5, 1965,;1hund0ncd.

5/1967 Levy et al. 260/327 3,349,115 10/1967 Wcil et all. 160/479 Primary ExaminerN0rma S. Milestone Attorney, Agent, or Firm-Frederick H. Rabin [57] ABSTRACT O-Phenylcarbamates, e.g., those of the formula R H, alkyl or alkenyl R alkyl or alkenyl R 4 alkyl, alkenyl, alkynyl R +R alkylene or alkenylene X H, aliphatic radical, halogen or nitro X O or S are biocides, e. g., insecticides.

1 Claim, No Drawings ll PHENYL CARBAMATES CROSS REFERENCE TO RELATED APPLICATIONS This is a division of application Ser. No. 197,474, filed on Nov. 10, I971, now US. Pat. No. 3,781,301, which is a continuation of application Ser. No. 2,445, filed on Jan. l2, 1970, now abandoned. Said application Ser. No. 2,445 was a continuation-in-part of application Ser. No. 728,335, filed on May I3, 1968, which, in turn, was a division of application Ser. No. 493,256, filed Oct. 5, I965, both now abandoned.

SUMMARY OF THE INVENTION The present invention concerns and has for its object the provision of new O-phenyl-carbamates of Formula I in which each of R and R is hydrogen, lower alkyl or lower alkenyl, each of X and X is hydrogen, a saturated or unsaturated lower aliphatic radical, halogene r nitro, X is oxygen or sulfur and each of R and R are alkyl, alkenyl or alkynyl or, when taken together, represent alkylene or alkenylene forming with the remaining moiety a 5 to 7 member'ed heterocycle, and in which R and R are unsubstituted or substituted by lower aliphatic radicals, halogeno, nitro or free or etherified hydroxy or mercapto, as well as of corresponding pesti'cidal preparations and methods for the preparation and application of these products. Said preparations are useful in the control of a wide variety of vegetable and animal pests.

DESCRIPTION OF THE PREFERRED EMBODIMENT The radicals R and R are identical or different and represent, for'example, hydrogen, methyl, ethyl nor i-propyl or allyl.

The moiety in 0- or mposition results from reacting the corresponding aldehyde, semiacetal or semimercaptal, for example, with methanol, ethanol, propanol. isopropanol, allyl alcohol, propargyl alcohol, 2- methoxyethanol, Z-methylmercaptoethanol, 2- chloroethanol, 2-bromethanol or 2-hydroxyethanethiol, or the corresponding semiacetal with methylmercaptan, ethylmercaptan, n-propylmercaptan, isopropylmercaptan, n-butylmercaptan. allylmercaptan, chlorallylmercaptan, dichlorallylmercaptan, propargylmercaptan, 2-methoxyethanethiol, or 2-methylmercaptoethanethiol. In case R and R when taken together, represent alkylene or alkenylene, said pentene-3,4-diol, 2-methyl-l,Z-butanediol, 2-methylsalicylaldehyde,

l,3butanediol, 2-methyl-2,3-butanediol, 2-methyl-2,4- butanediol, 2-methyl-3,4-butanediol, 2-ethyl-l,3- propanediol, l,4-dichloro-2-methyl2,3-butanediol, 4- bromo-2-methyl-2,3-butanediol, 4-iodo-2-methyl-2,3- butanediol, 2,2-dimethyl-l ,3-propanediol, 2,2- bischloromethyl-l ,3-propanediol, 2,4-hexanediol, 2-methyl-2,3-pentanediol, 3-methyl-2,4-pentanediol, 2,2-dimethyl-3,4-butanediol, l,5-hexadiene-3,4-diol, 2-et hanol-l-thiol, 2-propanol-l-thiol, 3-chloro-2- propanoll-thiol, 3-propanol-l-thiol. Accordingly, each of R1, and R is preferably lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy-lower alkyl, lower alkylmercapto-lower alkyl, halo-lower alkyl, hydroxylower alkyl, halo-lower alkenyl, or R and R when taken together, preferably lower alkylene, monoor di' halo, lower alkylene, lower alkoxy-lower alkylene, lower alkenyloxy-lower alkylene, lower alkynyloxylower alkylene, lower alkanoyloxy-lower alkylene, lower alkylmercapto-lower alkylene, halo-lower alkenylmercapto-lower alkylene, hydroxy-lower alkylene, nitro-lower alkylene, lower alkenylene, hydroxylower alkenylene or lower alkadienylene. The term lower" referred to above and hereinafter in connection with organic radicals or compounds respectively, defines such with up to 6 carbon atoms.

' The radicals X and X are identical or different and represent, for example, hydrogen, lower alkyl, e.g., methyl, lower alkoxy. alkenyloxy or alkynyloxy or -mercapto or haloalkenylmercapto, e.g. methoxy, isopropoxy, allyloxy, propargyloxy, methylmercapto, allylmercapto or chlorallylmercapto, halogeno, e.g. fluoro, chloro, bromo or iodo, trifluoromethyl, nitro, di-lower alkylamino or di-lower alkenylamino. In this series most preferred compounds are obtained when X and X each represents a hydrogen atom, a lower alkyl or a lower alkoxy radical. Accordingly, the above mentioned aldehydes, represent, for example, salicylaldehyde, 4-methyl salicylaldehyde. S-methylsalicylaldehyde, 4-methoxy-s alicylaldehyde, 4-

' isopropoxy-salicylaldehyde, 4-chloro-salicylaldehyde,

5-chloro-salicylaldehyde, 5-bromo-salicylaldehyde,' 5- methylmercapto-salicylaldehyde, 4-trifluoromethyl- S-nitro-salicylaldehyde, 4-

3 dimethylamino-salicylaldehyde, 3,5-dichlorosalicylaldehyde, 3,5dinitro-salicyaldehyde, 3- hydroxybenzaldehyde, 2-chloro-3hydroxybenzaldehyde, 6bromo-3-hydroxybenzaldehyde or S-hydroxy- 3-methylbenzaldehyde.

The compounds of the invention exhibit valuable properties, for example, biocidal, especially insecticidal and acaricidal properties. Furthermore, they act also as herbicides, bactericides, fungicides and molluscicides. lnter alia, these carbamates develop a very strong action, for example, against houseflies, aphids, caterpillars and beetles, for example, corn weavil and Colorado beetle. Their contact effect is far superior to that of the known active substance Carbaryl" (N- methyl-a-naphthylcarbamate).

They are not only suitable for use as herbicides, but when applied in a concentration that does not produce phytotoxic effects, they may also be used in plant protection since they develop an excellent effect against harmful microorganisms, for example against fungi, for

example Alternaria solani, Phytopthora infestans and ple, against Aspergillus species.

Particularly useful are compounds of Formula I in which each of R and R is hydrogen, lower alkyl or lower alkenyl, each of X and X is hydrogen, lower alklyl, lower alkoxy, lower alkenyloxy, lower alkynyloxy, lower alkylmercapto, lower alkenylmercapto, lower alkynylmercapto, lower haloalkenylmercapto, halogeno, trifluoromethyl, nitro, di-lower alkylamino or di-lower alkenylaniino, X is oxygen or sulfur and each of R and R, is lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy-lower alkyl, lower alkylmercapto-lower alkyl, halo-lower alkyl, hydroxylower alkyl, halo-lower alkenyl or R and R when taken together, represent lower alkylene, monoor dihalo-lower alkylene, lower alkoxy-lower alkylene, lower alkenyloxy-lower alkylene, lower alkynyloxylower alkylene, lower alkanoyloxy-lower alkylene, lower alkylmercapto-lower alkylene, halo-lower alkenylmercapto-lower alkylene, hydroxy-lower alkylene, nitro-lower alkylene, lower alkenylene, hydroxylower alkenylene or lower alkadienylene, forming with the remaining moiety a 5 to 7 membered heterocycle.

Especially suitable for insect control are the carbamates of Formula I wherein R, is hydrogen, R is lower alkyl, each of X, and X is hydrogen, methyl, chloro, bromo, trifluoromethyl or nitro, X is oxygen or sulfur and each of R and R is lower alkyl, lower alkenyl or lower alkynyl or R and R when taken together represent alkylene or alkenylene with 2 to 4 carbon atoms, forming with the remaining moiety a 5 to 7 membered heterocycle and being unsubstituted or substituted by halogen, nitro, hydroxy, lower alkoxy or lower alkenyloxy.

Preferred are compounds of Formulae ll and Ill in which X, is oxygen or sulfur and each of R and R, is lower alkyl, lower alkenyl or lower alkynyl or R and R when taken together, represent alkylene or alkenylene with 2 to 4 carbon atoms, forming with the remain ing moiety a 5 to 7 membered heterocycle and being unsubstituted or substituted by halogen, nitro, hydroxy, lower alkoxyor lower alkenyloxy.

Most preferred are compounds of the formula ll in which X is oxygen or sulfur and each of R and R is lower alkyl or R and R when taken together, represent alkylene or alkenylene with 2 to 4 carbon atoms. forming with the remaining moiety a 5 to 7 membered unsubstituted heterocycle and of Formula lV in which X is oxygen or sulfur and each of R,-, and R is hydrogen or lower alkyl.

Outstanding are the compounds of Formula IV, in which X is oxygen or sulfur and each of R and R is hydrogen or methyl.

The compounds of the invention are prepared, for example, by reacting a phenol of the formula V OR4 X; (W

with a reactive derivative or carbonic acid and with R,NHR

The reaction of the phenol with the reactive derivative of carbonic acid and the amine may be carried out in either sequence, depending to some extent on the constitution of the required final product. Accordingly, said phenol or an alkali metal salt thereof may be reacted, for example, with phosgene and the resulting chlorocarbonate or carbonate condensed with R,-N- H--R Alternatively, said amine may be first reacted with phosgene and the resulting carbamic acid chloride or (when R, or R represents hydrogen) the isocyanate readily formed from it, may be reacted with the phenol. Furthermore, a urethane derived from the amine, preferably an alkyl urethane, may be reacted with the phenol (transesterification). It is also possible to react an urea derived from the amine with the phenol preferably at a raised temperature.

The products so obtained are open-chain or cyclic acetals or mercaptals, depending on the stoichiometric propertions of the starting materials and on the valency of the alcohols or mercaptans. According to the size of the ring and the kind'of hetero atom present in the acetalized moiety, the carbamates ofthis invention may be designated as derivatives of l,3-dioxolan (from 1,2- glycols), of l,3-di0xan (from 1,3-glycols), of 1,3- dioxepan (from 1,4-glycols) or of 1,3-oxathiolans (from l,2-hydr0xymercaptans).

The starting materials used are known or, ifnew, can be prepared analogous to the method for the known products (cf. for example Houben-Weyl, Methoden der organischen Chemie, volume 7, part 1, Stuttgart 1945). For example, the phenols of Formula V are prepared by reacting an orthoor meta-hydroxy-benzaldehyde with a lower alcohol or mercaptan in the presence of an acid catalyst, for example zinc chloride, a mineral acid or paratoluenesulphonic acid. These reactions may also be carried out with aldehyde derivatives, for example oximes, aldehydanils or acetals (transacetalization). Another suitable route is the acetalization with the aid of ortho-formic acid esters, formimine ethers, dimethylsulphite or ortho-silicic acid esters in the presence of lower aliphatic alcohols. Another route leading to said phenols is the reaction of suitable halides with alkali metal or alkaline earth metal alcoholates.

Said acetalization may be performed in two stages, with the semiacetals or semimercaptals being formed in the first reaction stage. With different alcohols are used in the two reaction stages, mixed acetals, i.e., monothioacetals, are obtained.

When optically active alcohols or mercaptans are used, there may be prepared optically active phenols of the Formula V and from them optically activecarbamates'of the Formula 1. If its acetal moiety of cyclic and substituted, further isomerizing possibilities offer themselves. A carbamate of the Formula 1 whose acetal residue is monosubstituted may be obtained in the cis-form or trans-form. In general, the present process for the manufacture of said carbamates gives rise to mixtures of all possible isomers; these mixtures can be separated into their constituents by known methods, for example by crystallization. For the manufacture of the preparations of this invention to be used for pest control, however, the stereoisomer r'nixtures obtained in the manufacture of the active substances are generally used.

As mentioned in the beginning the present invention also provides pesticidal preparations comprising as the active ingredient at least one carbamate of the Formula I and, if desired, one of the following additives. Such additives are those commonly used in pesticidal preparations such as vehicles, solvents, diluents, dispersants, wetting agents,.adhesives, fertilizers and, if required, further pesticides. Corresponding spray solutions are prepared, for example, with petroleum fractions having a high to medium boiling range, for example-Diesel oil or kerosene, coal tar oil, or oils of vegetable or animal origin, as well as hydrocarbons, for example alkylated naphthalenes, tetrahydronaphthalene, if desired or required with the use of xylene mixtures, cyclohexanols ketones or chlorinated hydrocarbons for example trichloroethane or tetrachloroethane, trichloroethylene or trior tetrachlorobenzenes. It is advantageous to use organic solvents having a boiling point above 100C.

it is especially advantageous to prepare aqueous forms of application from emuslion concentrates, pastes or wettable spray powders by addition of water. Suitable emulsifiers or dispersants are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids with a long-chain hydrocarbon residue of about to 20 carbon atoms with ethylene oxide, for example the condensation product from octadecyl alcohol with 25 to 30 mols of ethylene oxide, or of commercial oleylamine with Aldehyde Glycol 1 Salicyluldehyde 1.2-propanediol Cyclic acetal b.p.85C/0.03mm Hg mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide. As suitable anionic emulsifiers, there may be mentioned the following: The sodium salt of dodecylbenzosulphonic acid, the potassium of tri ethanolamine salt of oleic acid or of abietic acid or of a mixture of these two acids, or the sodium salt of a petroleumsulphonic acid. Suitable cationic dispersants are quaternary ammonium compounds, for example cetyl pyridinium bromide and dihydroxyethyl benzyl dodecyl ammonium chloride.

For the manufacture of dusting and casting preparations, thre may be used as solid vehicles: talcum, kaolin, bentonite, calcium carbonate, calcium phosphate or coal, cork meal, wood meal or other materials of vegetable origin. It is also very advantageous to manufacture the preparations in the form of granulates. The various forms of application may contain the conventional additives that improve the distribution, the adhesion, stability to rain or the penetration; as such sub stances there may be mentioned fatty acids, resin, glue, casein and alginates.

The preparations of this invention may be used by themselves or in conjunction or admixture with conventional pesticides, especially insecticides, acaricides,

nematocides, bactericides, fungicides, herbicides and the like.

The following Examples are intended to illustratethe invention and are not to be construed as being limitations thereon. Temperatures are given in degrees Centigrade, and all parts or percentages wherever given are such by weight.

EXAMPLE 1 a. ortho-( l,3-dioxolan-2-yl)-phenol Hg pressure and melted at 67 to 70C.

b. ortho-(1,3-dioxolan-2-yl)-phenyl-N-methyl-carbamate A solution of 50 parts of ortho-(1,3-dioxolan-2 yl)- phenol in 300 partsby volume of dry toluene was mixed with about 0.2 part by volume of triethylamine,

and 20 parts of methylisocyanate were dropped into this solution at room temperature. The temperature rose gradually to 31C. The mixture was kept for 1 day at room temperature. The product was filteredoff and crystallized from toluene; it melted at 111 to 1 14C.

} EXAMPLE '2 When glycols (polyols) were reacted with unsubstituted or substituted orthoor metahydroxybenzaldehydes, thercondensation as described "inExample 1 lead to cyclic acetals. When these acetals were reacted with methylisocyanate, they furnished, for example, the following carbamates:

Carbamate ortho-( 4-methyl-l .3-dioxolan-2-yl )-phenyl- N-methyl-carbamate (crystallizes gradually) Continued No. Aldehyde Glycol Cyclic acetal Carbamate 2 do. 2,3-butanediol h.p.86C/0.07mm Hg ortho-t4.5-dimethyl-l.3-dioxolan-2-yl)- (commercial phenyl-N-methyl-carhamate. m.p. 70 105C mixture of stereoisomers) 3 do. l-butene-3.4-diol h.p.82C/0.08mm Hg ortho-(4-vinyl-l.3-dioxolan-2-yl)-phenyl- N-methyl-carbamate 4 do. glycerol-a-monob.p.l1l 114C ortho-(4-eh1oromethyl-l.3-dioxolan-2-yhchlorohydrin 0.3mm Hg phenyl-N-methyl-carhamate. m.p about 30 to 70C 5 do. glycerol m.p.148 to 149C ortho-(4-hydroxymethyl-1.3-dioxolan-2-yl)- front acetonitrile phenyl-N-methyl-carbamate. or

ortho-(S-hydroxy-l .3-dioxan-2-ylPphenyl- N-methyl-carbamate. m.p.l to 134C. As hy-product the corresponding hisN- methyl-carbamate melting at 170 to 172C was obtained. 6 do. 1.3-propanediol h.p.92 to 96C ortho-(1.3dioxan-2-yl)-phenyl-N-methyl- 0.01mm Hg carhamate. M.p.125 to 127C (from toluene) 7 do. 1.3-hutanediol b.p.89 to 95C ortho-(4-methyl-1.3-dioxan-2-yl)-phcnyl- 006mm Hg N-methyl-carbamate. M.p.l46 to 148C (from acetonitrile) 8 do. neopcntylglycol h.p.90C/0.06mm ortho-(5.5-dimethyl-l ,3-dioxan-2-yl)-phenyl- Hg m.p.58 C N-methyl-carbamate. M.p.l22 to 124C (from carbon tetrachloride) 9 do. 3-methyl2.4 h.p.93C/0.0Imm Hg ortho-(4,5,6-trimethyl-l,3-dioxan-2-yl)- pent-andediol phenyl-N-melhylcarbamate m.p. 118 to 136C 10 do. 2-methyl-2-nitro-1. m.p.90 to 93C ortho-tS-methyl-S-nitro-l.3-dioxan-2-yl)- 3-propane'diol (from ether+ phenyl-N-melhyl-carbamate m.p.l31 133C cyclohexane) (from isopropanol) 11 do. 2-butene-1.4- b.p.87C/0.03mm Hg ortho-t1.3-dioxep-5-en-2-yl)-pheny1-N- diol methyl-carhamate m.p.94 C (from toluene) 12 4-methylsalicylethyleneglycol b.p.98C/0.02mm Hg; ortho-(1.3-dioxolan-2-yl)-meta-methylphenylaldehyde I crystallizes N-methyl-carhamate m.p.96 to 99C (from toluene) l3 S-methylsalicyldo. h.p.9596C ortho-t1.3-dioxolan-2-yl)-para-methylphenylaldehyde 0.01mm Hg N-methyl-carhamate m.p.104 to 106C (from carbon tetrachloride) 14 mixture 01'4- and 1.2-propanediol b.p.90C/0.7mm Hg ortho-(4-methyl-1.3-dioxolan-2-yl)-metaand 6-trit'luorometa'-trifluoromethylphenyl-N-ntethyl methyl-salieylcarhaniatc (viscous oil) aldehyde l5 S-ehlorosalieyh ethylcneglycol m.p.1l2( (from para-chloro-ortho-t1.3-dioxolan-2-yll-phenylaldehyde toluene) N-niethyl earhamate m.p.l09 l 12C (from benzene+hexane) [6 mixture of 4- and 1.2-propanediol h.p.93-9llC/0.0lmn1 Hg ortho-(4-methyl-l .3-dioxolan-2-yl)- o-chlorosalicylnictaand ineta'-chlorophenyl-N- aldehyde methyl carbamate. m.p. about 90 to C 17 S-hromosalicylethyleneglycol m.p.8lC (front hexane) para-bromo-ortho-(1.3-dioxolan-2-yllaldehyde phenyl-N-methyl-carbamate. m.p.

107 to 109C (from ethylene chloride) 18 3.5-dibromo-salicyldo. b.p.l45C/0.l7mm Hg ortho. para-dihromo-ortho'(1.3-dioxoaldehyde m.p.60 to 64C lan-2-yl)-phenyl-Nmethyl-carbamate m.p.135 139C (from acetonitrile) 19 3.5-dinitrodo. m.p. 134-140C (from ortho. para-dinitro-ortho'-(1.3-dioxosalicylaldehyde chlorobenzene) lan-2-yl)-phenyl-N-methyl-carbamate m.p.149 155C (from acetone) 20 meta-hydroxydo. b.p.1l3 to C/0.03 meta-t1.3-dioxo1an-2-yl)-phenyl-N- henzaldehyde mm Hg methyl-carbamate. m.p.73 to 77C (from toluene) 2| meta-hydroxy- 2.3-butanediol h.p.115C/0.1mm Hg meta-(4.5-dimethyl-1.3-dioxolan-2-yl) henzaldehyde (commercial) phenyl-N-methyl-carhamate. viscous oil +)4(6)-tril'luurumethyl-salicylaldehyde can lie prepared from 3-tril'luoromethylphenol by the method of J. C. Dull" (J. Chem. Soc. 1941. page 547. Free. Iowa Acad.

Sci. 52. page 191 tl945)I.l1bO1lS at 77 to 110C under 14mm HG pressure.

EXAMPLE 3 salicylaldehyde diethyl acetal A mixture of 122 parts of salicylaldehyde, 180 parts of orthoformic acid ethyl ester and parts of anhydrous ethanol was mixed with 1 ml of concentrated hydrochloric acid, whereupon the whole heated up spontaneously. After a short time, the solution was heated to the boil and then evaporated under vacuum, and the residue distilled under a high vacuum. The product passed over at 80C under 0.15mm Hg pressure.

ortho-(diethoxymethyl)-phenyl-N-methyl-carbamate A A solution of 138 parts of salicylaldehyde diethyl acetal. 46 parts of methylisocyanate and 0.5 part of tri- EXAMLPLE 4 0rtho-(1,3-oxathi0lan-2-yl)-phenol 82 Parts of Z-mercaptoethanol were mixed with 0.5

part by volume of concentrated hydrochloric acid and then dropwise with 122 parts of salicylaldehyde; the temperature of the mixture rose. The reaction mixture was stirred for 1 hour at room temperature, then diluted with 500 parts by volume of ether and washed with sodium bicarbonate solution and then with water until the washings ran neutral. The solution was dried over anhydrous sodium sulphate, filtered and evaporated.

The viscous residue was heated under a high vacuum at a bath temperature of 160C, and the volatile phase was condensed. The condensate was then fractionated. At 112C under a pressure of 0.05mm Hg, the ortho- (1,3-oxathiolan-2-yl)-phenol formed passed over and crystallized on standing. 1t melted at 72 74C.

ortho-(1,3-oxathiolan-2-yl)-phenyl-N-methy1- carbamate Parts of methylisocyanate and 0.1 part of triethylenediamine were added to a solution of 37 parts of ortho-(l.3-oxathiolan-2-yl)-phenol in 100 parts by volume of dry toluene. The mixture was moderately cooled to maintain its temperature below 35C. After a few hours, the resulting crystalline product was'filtered off and recrystallized from toluene or carbon tetrachloride. It melted at 108 to 109C.

EXAMPLE 5 ortho-para-dinitro-ortho-(1,3-dioxolan-2-yl)-phenol A mixture of 196 parts of 3,5-dinitrosalicylaldehyde, 70 parts of glycol and 500 parts by volume of benzene was boiled in the presence of 1 part of anhydrous zinc chloride and 1 part by volume of concentrated phosphoric acid in a circulation distillation apparatus, until water was no longer being eliminated. After cooling, the product were filtered off and crystallized from chlorobenzene; it melted at 134 to 140C.

ortho,para-dinitro-ortho-(1,3-dioxolan-2-yl)-phenyl- N,N-dimethyl-carbmate 11.3 Parts of dimethylcarbamic acid chloride were added to a mixture of 25.6 parts of ortho,para-dinitroortho-(l,3-dioxolan-2-yl)-phenol, 200 parts by volume of chlorobenzene and 25 parts of triethylamine. The solution was heated for 5 hours at 130C, allowed to cool, filtered, washed with 2N-sodium carbonate solution and evaporated. The residue was crystallized from alcohol. The product melted at 141 to 142C.

EXAMPLE 6 Dusting Agent Equal parts of an active substance described in Examples 1 to 5 were mixed with precipitated silica and finely ground. When this powder is mixed with kaolin or talcum, it may be used in the form of dusting preparations having the desired concentration of active substance. ln general, preparations containing 1 to 5% of active substance are preferred.

Spray Powder To manufacture a spray powder, the following ingreclients, for example, were mixed and then finely ground: 50 parts of an active substance of Examples 1 to 5 parts of l-lisil (highly adsorbent, precipitated silica) .25 parts of bolus alba (kaolin) 3.5 of a reaction product from para-tertiary octylphenol and ethylene oxide 1.5 parts of sodium l-benzyl-2-stearylbenzimidazole-6,3 '-disulphonate.

Emulsion Concentrate EXAMPLE 7 The active substance of Example 1 and the active substance Carbaryl were subjected to a comparative test to establish their contact effect against houseflies and corn weavils. The new substance displayed a much greater, distinct contact-insecticidal effect.

When applied in a concentration of 0.04% in the control of aphids (aphis fabae) on young bean plants, it was found that after 2 days the active substance of Example 1 had completely destroyed the aphids. It was found to have a good diffusion and distinct systemic effect.

Carbaryl was found to be ineffective in those tests. Carbaryl is the common name for l-naphthyl-N-methyl-carbamate.

The above-mentioned active substance is active in limit concentrations of 1.2 parts per million against aedes larvae (24 hours).

The compound was also tested in dust form against various pests (1%, 2g/m 20kg per hectare) and the following results were recorded:

after after 6 hours 24 hours Phyllodronia germanica Porcellic scaber 100% Formica rufa 100% A topical test on larvae of Periplaneta americana revealed in an evaluation made 24 hours later the following limit concentrations of active substance compared with various commercially available phosphoric acid propen-2-yl)-phosphate 0,0-dimethyl-O-t4-methylmercapto-3-methy1-pheny1)- thinophosphate.

The active substance of Example 1 acts also against spider mites (Tetranychus urticae).

When tested as a stomach poison on Carausius, the said active substance displayed a good effect, against Prodenia a moderate to good effect and against Gastroidea rather a good effect.

EXAMPLE 8 Contact action againstMusca domestica.

Compound knock down effect Example 1 100 Example 2.1 100 Example 2.2 100 Example 4 90 7:

EXAMPLE 9 Action against spider mites (Tetranychus urticae). 12 hours prior to the testing treatment dwarf bean plants (Phaseolus vulgaris) in the two-leave stage were infested with cultured mites. At the time of spraying the plants with an 800 ppm emulsion of active ingredient by means of a chromatographic atomizer all possible living stages of mites were found on the plants. The evaluation was made after 2 and 7 days.

Compounds killing in after 2 days 7 days Example 1 80 100 Example 2.1 80 80 Example 2.2 60 80 EXAMPLE Compound killing effect after 3 hours Example 1 100 2 Example 2.1 100% Example 2.2 100 7r Example 4 100 If EXAMPLE 1 1 Action against bugs (Cimex lactularius). This test was carried out according to the statement in Example 10 with the following exceptions: the acetonic solution (1 ml of a 10 ppm solution of active ingredient) was applied to filterpaper which was placed on the bottom of a Petri dish of 9 cm of diameter. Ten adult bugs were put on the paper and exposed for 48 hours to the action of the active ingredient. The test was repeated twice with the following results. 20 killed bugs (twice 10 bugs) are indicated as 100%.

compounds killing effect after 48 hours Example 1 7r Example 2.1 7: Example 2.2 100 7:

EXAMPLE 12 Action against cockroaches (Periplaneta americana and Blatta orientalis).

A 5% dusting agent was prepared according to Example 6 using as carrier exclusively talcum. By mixing equal parts of dusting preparataion and talcum a dilution series with progressive dilution was made in which every step contained half the quantity of active ingredient contained in the preceding step. Accordingly, the series thus made had a content of active ingredient of 5, 2.5, 1.2, 0.6, 0.3, 0.15, 0.08 which corresponds to an amount of 100, 50, 25, 12.5, 6.2, 3.1, 1.5 mg of active ingredient per m when 2 g of dusting preparation are applied. The test was carried out on green filter paper by means of a bell-shaped application apparatus and an amount of dusting preparation which corresponds to 2 g per m and was applied with compressed air. The test animals which were in the fifth larvae stage (L-5) were put on the treated paper surface. Evaluation took place 24 hours later and the results listed below indicate the minimum concentration necessary to provide a 100 killing effect within 24 hours. 8n

Minimum concentration in mg providing 100% killing within 1. Ortho-( l ,3-Dioxep-5-en-2-yl)-phenyl-N- methylcarbamate.

* k OI UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,856,816 Dated December 24, 1974 Inventoflg) Erwin Nikles, Volker Dittrich & Ladislaus Pinter It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The following should appear on the cover page:

"The term of this patent subsequent to December 25, 1990,

has been disclaimed".

Sighed and Scaled this.

fourteenth Day Of October 1975 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Patents and Trademarks 

1. ORHTO-(1,3-DIOXEP-5-EN-2-YL)-PHENYL-NMETHYLCARBAMATE. 